1. Field of the Invention
The present invention relates to a process for preparing a dental prosthesis from a composite resin.
2. Description of the Conventional Art
As the restoration of teeth are generally carried out by a restoration method using a dental prosthesis, in which, after preparation of a cavity, or after core construction of an abutment tooth, an impression (counterdie of tooth) is taken, a gypsum model (duplicate of tooth) is prepared based on the impression by using a gypsum or the like, a dental prosthesis is prepared based on the cast in a manner as described later, and the dental prosthesis is cemented to a tooth by using an adhesive such as a dental cement; and by a method of filling restoration, in which a dental composite resin is directly filled in a cavity and then polymerized and cured by chemical polymerization or light-polymerization to effect restoration.
In the case of dental prostheses such as inlays and crowns, there is widely employed a method called as a lost wax casting process, in which a dental wax is applied on a gypsum model to prepare a wax pattern having the same shape as an objective dental prosthesis; the wax pattern is invested in a refractory investment; after setting the investment, the wax pattern is heated and burnt in an electric furnace; a dental alloy is cast using a cast molding thus obtained; and the resulting cast material is excavated from the investment, followed by triming and polishing to prepare a metallic dental prosthesis.
In cases of inlays, crowns, etc., particularly in cases where aesthetics in, for example, restoration of anterior teeth, are required, restoration by means of dental prostheses such as ceramic inlays, resin facing crowns, porcelain facing metal crowns, and all ceramic crowns is carried out.
Specifically, in the case of dental prostheses such as ceramic inlays and all ceramic crowns, a refractory duplicated model is prepared by using a refractory material, a dental ceramics powder is built up and formed on the refractory duplicated model through manual works by a dental technician, and after firing, the refractory duplicated model is removed, followed by forming the surface characterization and polishing to prepare a dental prosthesis. Further, in the case of resin facing crowns or porcelain facing metal crowns, a resin having a tooth crown color is built up and polymerized for application on a labial surface of a metal crown prepared by the lost wax casting process, or a porcelain having a tooth crown color is built up and fired and then subjected to forming the surface characterization and polishing, to prepare a dental prosthesis.
However, in the case of dental filling restoration using composite resins, since the dental composite resin is filled in a cavity and immediately thereafter polymerized and cured, the strength is often insufficient. Further, since the unpolymerized monomer likely remains, a problem of pulp irritation is also pointed out. In addition, in the case of metallic dental prostheses, since a metal color is exposed on a surface of the dental prosthesis, a problem of aesthetics arises. Moreover, in the case of dental prostheses such as ceramic inlays, all ceramic crowns, resin facing crowns, and porcelain facing metal crowns, since a high-level technique is required for building up and forming through porcelain works, there is a defect that not only a lot of skill by a dental technician but also a long period of time and much expenses are required.
On the other hand, Japanese Patent Laid-Open No. 227400/1995 discloses a process for preparing a denture base by charging under a high pressure a thermoplastic resin, a thermosetting resin, etc. into in a mold, in which a process for preparing a dental prosthesis such as an inlay and a crown is also described. This process is a process in which a denture base is subjective and is formed by charging under a high pressure a thermoplastic resin into a mold, with thermoplastic resins having good fluidity, such as polycarbonates, polysulfones, polyethersuflones, and acrylic resins, being used. However, even when these thermoplastic resins are compounded and reinforced with glass fibers, etc., the strength is still insufficient. Accordingly, it was hard to say that these thermoplastic resins have a performance sufficient for utilizations of the preparation of dental prostheses such as crowns, which are required to have a mechanical strength and wearing durability.
The invention is aimed to provide a process for preparing a dental prosthesis, particularly suitable for an inlay, a crown, etc., which is not only superior in aesthetics and mechanical properties but also is free from any fear of pulp irritation by unpolymerized monomers.
We, the present inventors, investigated that when, by applying a technique of injection molding or pressure injection, which has hitherto been employed for the preparation of dentures, artificial teeth, etc., a composite resin having a superior strength as compared with thermoplastic resins such as polysulfones and being, superior in esthetics to metal materials, is charged under pressure into a mold and subjected to polymerization under heat and pressure, a dental prosthesis that is free from the remaining of unpolymerized monomers and superior in mechanical properties can be prepared, leading to the accomplishment of a process for preparing a dental prosthesis according to the invention.
Specifically, the invention is to provide a process for preparing a dental prosthesis comprising preparation of a wax pattern of an objective dental prosthesis based on a duplicated model having an intraoral shape, investment of the wax pattern in an investment material, and removal of the wax pattern to prepare a mold, wherein a composite resin is charged under pressure into the mold, and the composite resin is cured under heat and pressure.
In carrying out the process for preparing a dental prosthesis according to the invention, first of all, a tooth on which an objective dental prosthesis is applied subjected to preparation of a cavity or core construction of the tooth, and an impression of its shape is then taken by using a dental impression material, etc. At this time, any materials can be used without particular limitations as the impression material to be used, so far as they can preciously reproduce the shape of the tooth. However, impression materials that are popularly used in the dentistry field are preferred because they are superior in precision and handling, with dental silicone impression materials being particularly preferred.
Subsequently, a dental gypsum, a dental investment or the like is poured into the taken impression and set to prepare a duplicated model having an intraoral shape. Then, a wax such as a dental wax is applied on the duplicated model to prepare a wax pattern of an objective dental prosthesis, and the thus completed wax pattern is attached to a sprue made of a wax or a metal in a usual manner.
Subsequently, the wax pattern is invested, either alone or together with a duplicated model, in a heat-resistant vessel such as a casting ring, by using an investment material. As the investment material, in the case where the viscosity of the composite resin to be charged under pressure is low, and the maximum charging pressure is low as 0.5 to 5 MPa, casting investment materials that are used in the dentistry can be used. Further, when a dental gypsum or the like is used, it is possible to apply a higher pressure. Moreover, in the case where a charging pressure exceeding 5 MPa is required, it is preferred to use a dental improved stone that is durable to a higher pressure.
After setting of the investment material, the whole of the heat-resistant vessel is heated according to a customary manner, and the internal wax pattern is removed to prepare a mold. When the wax pattern cannot be burnt and removed by burning as in the case where a gypsum is used as the investment material, the wax is removed by using hot water or upon heating in an air pressure pot to prepare a mold.
Thereafter, the heat-resistant vessel is set on a pressure injection apparatus, and a composite resin is charged under pressure thereinto. The charging pressure is 0.5 to 30 MPa, and preferably 5 to 20 MPa. When the charging pressure is lower than 0.5 MPa, the composite resin may not spread into details of the mold. In contrast, when it exceeds 30 MPa, the cast and the dental gypsum for investment are in danger of breakage.
In the case where it is difficult to charge under pressure the composite resin because of its high viscosity, it is possible to charge under pressure the composite resin after softening the composite resin upon heating at 60 to 90xc2x0 C. and further heating the heat-resistant vessel at 120 to 150xc2x0 C. to adjust the fluidity. When the temperature at the time of charging under pressure is lower than 60xc2x0 C., the effect for increasing the fluidity cannot be obtained. In contrast, in the case that the temperature exceeds 90xc2x0 C., the polymerization and curing of the composite resin are rapidly promoted, there is a possibility of the polymerization and curing to occur before the charging under pressure, and hence, such is not preferred.
At the time of charging under pressure, in order that the composite resin spreads into the details without causing the breakage of the investment material, it is necessary to adjust the time, pressure and temperature of the charging under pressure of the composite resin.
After the charging under pressure, the composite resin is pressurized and heated to effect polymerization and curing. At the time of the pressurization and heating, it is preferred that the pressure is about 70 to 100% of that upon charging under pressure, whereas the heating temperature is from 95 to 150xc2x0 C.
The time of the pressurization and heating varies depending upon the pressurization and heating conditions and the polymerization properties of monomers or oligomers to be used for the composite resin, such as (meth)acrylates, but it is usually 2 to 30 minutes, and preferably 5 to 15 minutes.
After pressurizing and heating the composite resin to effect polymerization and curing, the composite resin is cooled as it is in a pressurized state and then reduced in the pressure. The retention of the pressure is necessary for spreading the composite resin into the details of the dental prosthesis as well as correcting the polymerization shrinkage of the composite resin.
As the apparatus for charging under pressure, an apparatus for charging under pressure, which is usually used in the dentistry, and in which a dental material for denture base used for the preparation of a denture base or the like can be charged into a pressure-resistant vessel under a pressure of 0.5 to 30 MPa, can be used.
The composite resin that is used in the invention is a composite resin comprising a (meth)acrylate arbitrarily compounded with one or more than two inorganic, organic or inorganic-organic composite fillers and further added with a heat polymerization catalyst. Namely, the composite resin used in the invention is compounded with a heat polymerization catalyst suitable for the heat polymerization under pressure and adjusted so as to be suited for the charging under pressure instead of a light-polymerization catalyst for dental composite resins, which has hitherto been used mainly for filling and restoration in the dentistry.
As the (meth) acrylate, those which are generally used for the dental composite resin can be used, and in addition to monomers, oligomers and the like can be used. Examples of monomers include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxy-1,3-dimethacryloxypropane, n-butyl methacrylate, isobutyl methacrylate, hydroxypropyl methacrylate, tetrahydrofurfuryl methacrylate, glycidyl methacrylate, 2-methoxyethyl methacrylate, 2-ethylhexyl methacrylate, benzyl methacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, tetraethylene glycol dimethacrylate, pentaerythritol trimethacrylate, trimethylolmethane trimethacrylate, pentaerythritol tetramethacrylate, di-2-methacryloxyethyl-2,2,4-trimethyl hexamethylene dicarbamate, 1,3,5-tris[1,3-bis(methacryloyloxy)-2-propoxycarbonylaminohexane]-1,3,5-(1H,3H,5H)-triazine-2,4,6-trione, 1,6-methacrylethyloxycarbonylaminohexane, 1,3-methacrylethyloxycarbonylaminohexylaminocarbonyloxy(3-methyl)propane, and 1,6-methacrylethyloxycarbonylaminohexylaminocarbonyloxy(3-methyl)propyloxycarbonylaminohexane, as well as corresponding acrylates thereto. Further, examples of oligomers include a urethane oligomer comprising 1,3-butylene glycol, hexamethylene diisocyanate and 2-hydroxyethyl methacrylate and a urethane oligomer comprising 2,2-di (4-hydroxycyclohexyl)propane, hexamethylene diisocyanate and 2-hydroxyethyl methacrylate, as well as corresponding acrylates thereto. These monomers or oligomers can be used singly or in admixture of two or more thereof.
Examples of the filler include various glasses such as barium glass, alumina glass and potassium glass, and powders of silica, feldspar, and quartz. Further, inorganic-organic composite fillers obtained by mixing a monomer with an inorganic filler and curing the mixture, followed by pulverization, can also be used. These fillers are preferably subjected in advance to surface processing with a silane substance, and the surface processing is carried out by a known silane processing process.
Of these, a composite resin containing 30 to 80% by weight, and preferably 60 to 80% by weight of at least one filler selected from a glass powder having a mean particle size of 0.02 to 10 xcexcm, ultrafine powdered silica having a mean particle size of 0.02 to 0.04 xcexcm, and an inorganic-organic composite filler obtained by mixing a monomer with ultrafine powdered silica having a mean particle size of 0.02 to 0.04 xcexcm and curing the mixture, followed by pulverization, is particularly preferred because the strength and the abrasion resistance after curing are high, and the viscosity is suitable for charging under pressure into the mold when the temperature is 60 to 90xc2x0 C.
As the heat polymerization catalyst are preferred azo compounds such as azobisisobutyronitrile and organometallic compounds such as tributylboron. Further, diacyl peroxides containing an aromatic ring and peroxy esters that are seemed to be an ester of perbenzoic acid, such as benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, m-tolyl peroxide, t-butyl peroxybenzoate, di-t-butyl peroxyisophthalate, 2,5-di-methyl-2,5-di(benzoyl peroxy)hexane, and 2,5-di-methyl-2,5-di[(o-benzoyl)benzoyl peroxy]hexane, can be used.
These heat polymerization catalysts can be used singly or in admixture of two or more thereof. When a compounding amount of the heat polymerization catalyst is less than 0.03% by weight to the composition, a sufficient effect is hardly obtained. In contrast, while varying depending upon the type and compounding amount of the monomer used, when the heat polymerization catalyst is compounded in an amount exceeding 3% by weight, the polymerization reaction proceeds before the heating will be carried out sufficiently, whereby the composite resin may not be charged under pressure into the mold.
With respect to the composite resin used in the invention, in the case where the compounding amount of the ultrafine powdered silica exceeds 10% by weight, since the flow of the paste charged and the discharge of porosities become poor, an air vent for exhaust maybe provided in the investment material, if desired. Further, while the composite resin used in the invention is usually colored into a tooth crown color and used for the preparation of a dental prosthesis such as an inlay and a crown, it is also possible to prepare a denture base having a higher strength by coloring it into a gingival color.
As the heat-resistant vessel surrounding the mold and to be installed on the pressure injection apparatus, a dental flask, which is used for the preparation of a denture in the dentistry, and the like can be used, in addition to the above-described casting ring. In the case where the dental flask is used, the investment is carried out according to a method for use of the investment of a wax pattern using a dental flask, which is generally employed in the preparation of a denture, and the installation of a sprue is carried out, and then, the composite resin is charged under pressure according to the method as described above.
In the case where the dental flask is of a separation type, since the sprue is set along the gypsum and investment from the wax pattern to the composite resin inlet, it is preferred that the cross-sectional shape of the sprue is rectangular, half-round, etc. As a method for the removal of the wax pattern, a method in which the vessel is once separated, the wax pattern is subjected to complete wax removal by using hot water, etc., and then, the heat-resistant vessel is again assembled, is suitable.
In the case where a dental flask is used as the heat-resistant vessel, and a dental improved stone is used as the investment material, a pressure over 10 MPa can be applied. Accordingly, it is possible to improve the strength and abrasion resistance of the composite resin after the polymerization.
According to the process of the invention, dental prostheses such as inlays and crowns, which are superior in aesthetics and mechanical properties and free from pulp irritation by the unpolymerized monomer, can be easily prepared. As a matter of course, the process of the invention can be applied to the preparation of a denture base.
The process for preparing a dental prosthesis according to the invention will be described more specifically with reference to the following Examples.
Tests were carried out with respect to dental prostheses of the following Examples 1 to 4 and Comparative Examples 1 and 2, as prepared by adding 100 parts by weight of each of composite resins having the following compositions with 0.1 part by weight of iron oxide, tri-iron tetroxide, titanium dioxide, chromium oxide, or the like for the purpose of coloring it into a tooth crown color as well as that as prepared by using a commercially available composite resin. The results obtained are summarized and shown in Table 1.
(Composite Resin I)
As the (meth)acrylate:
14.6% by weight of di-2-methacryloxy-2,2,4-trimethyl hexamethylene dicarbamate (hereinafter abbreviated as xe2x80x9cUDMAxe2x80x9d) 5.0% by weight of a mixture (a trade name: Art Resin SH-101, made by Negami Chemical Industrial Co., Ltd., hereinafter abbreviated as xe2x80x9cSE-101xe2x80x9d) consisting of 1,6-methacrylethyloxycarbonylaminohexane, 1,3-methacrylethyloxycarbonylaminohexylaminocarbonyloxy(3-methyl)propane and 1,6-methacrylethyloxycarbonylaminohexylaminocarbonyloxy-(3-methyl)propyloxycarbonylaminohexane; and 5.0% by weight of tetraethylene glycol dimethacrylate (hereinafter abbreviated as xe2x80x9cTEGDMAxe2x80x9d)
As the filler:
45% by weight of colloidal silica having a mean particle size of 0.04 xcexcm as an inorganic filler (a trade name: Aerosil OX-50, made by Nippon Aerosil Corporated, hereinafter abbreviated as xe2x80x9cOX-50xe2x80x9d) and 30% by weight of barium glass having a mean particle size of 0.5 xcexcm as a glass powder
As the heat polymerization catalyst:
0.4% by weight of benzoyl peroxide
(Composite Resin II)
As the (meth)acrylate:
29.8% by weight of UDMA and 7.0% by weight of SH-101
As the filler:
63% by weight of OX-50 as an inorganic filler
As the heat polymerization catalyst:
0.2% by weight of benzoyl peroxide
(Composite Resin III)
As the (meth)acrylate:
16.3% by weight of UDMA and 8.0% by weight of TEGDMA
As the filler:
3% by weight of colloidal silica having a mean particle size of 0.016 xcexcm as an inorganic filler (a trade name: Aerosil R-972, made by Nippon Aerosil Corporated, hereinafter abbreviated as xe2x80x9cR-972xe2x80x9d) and 72% by weight of fluoroaluminosilicate glass as a glass powder (prepared by weighing 25.0 g of alumina, 27.7 g of calcium carbonate, 15.2 g of aluminum phosphate, 13.3 g of aluminum fluoride, and 11.7 g of silica sand, respectively, mixing them with each other, charging the mixture into a platinum crucible, placing the crucible in an electric furnace, elevating the temperature in the furnace to 1,250xc2x0 C. over about 3 hours to melt the mixture, keeping that temperature for 2 hours to clarify a molten glass, and quenching and pulverizing it to adjust it so as to have a mean particle size of 1.0 xcexcm)
As the heat polymerization catalyst:
0.7% by weight of benzoyl peroxide
(Composite Resin IV)
As the (meth)acrylate:
21.3% by weight of UDMA and 10.0% by weight of TEGDMA
As the filler:
16% by weight of OX-50 as an inorganic filler and 52% by weight of a powder as an inorganic-organic composite filler {prepared by mixing 45% by weight of a powder obtained by subjecting colloidal silica having a mean particle size of 0.04 xcexcm (a trade name: Aerosil OX-50, made by Nippon Aerosil Corporated) to surface processing with an ethanol solution of 10% by weight of xcex3-mehtacryloxypropyl trimethoxysilane in a customary manner, with 55% by weight of a solution of 1 part by weight of 2,2xe2x80x2-azobisisobutyronitrile dissolved in 100 parts by weight of a monomer mixing solution consisting of 19 parts by weight of UDMA, 13 parts by weight of 1,3,5-tris-[1,3-bis(methacryloyloxy)-2-propoxycarbonylaminohexane]-1,3,5-(1H, 3H, 5H) triazine-2,4,6-trione, and 13 parts by weight of neopentyl glycol dimethacrylate, heat curing the mixture, and pulverizing it to adjust it so as to have a mean particle size of 10 xcexcm}
As the heat polymerization catalyst:
0.7% by weight of benzoyl peroxide